Control of bacteria and fungi with n-(3-trifluoromethyl-4-chlorophenyl)-carbamates

ABSTRACT

THE INVENTION RELATES TO COMPOUNDS OF THE GENERAL FORMULA   1-CL,2-(F3C-),4-(R1-O-CO-NH-)-BENZENE   WHEREIN R1 REPRESENTS AN ARALKYL OR ARALKENYL RESIDUE OR A PHENYL RADICAL HAVING 4 OR 5 SUBSTITUENTS OR A 5- TO 6MEMBERED HETEROCYCLE WHICH MAY BE BOUND OVER AN ALKYL RESIDUE USED FOR COMBATING VARIOUS TYES OF PESTS, PREFERABLY BACTERIA AND FUNGI.

United States Patent 01 Patented July 2, 1974 US. Cl. 424-300 9 ClaimsABSTRACT OF THE DISCLOSURE The invention relates to compounds of thegeneral formula wherein R represents an aralkyl or aralkenyl residue ora phenyl radical having 4 or substituents or a 5- to 6- memberedheterocycle which may be bound over an alkyl residue used for combatingvarious types of pests, preferably bacteria and fungi.

This is a division of application Ser. No. 796,571, filed Feb. 4, 1969,now US. Pat. No. 3,676,457.

The present invention provides pesticidal preparations, especiallypreparations of combating bacteria and fungi, which comprise, as activecomponent, a compound of the formula in which R represents an aralkyl oraralkenyl radical or a phenyl radical having four or five substituentsselected from halogen, an alkyl, alkoxy and/or nitro group, or a 5- tofi-membered heterocyclic radical that may be optionally bound over analkyl radical. The preparation may contain one or more of the followingadditives: a solvent, a diluent, a dispersant, a wetting agent, anadhesive as well as other known pesticides.

In a narrower sense, compounds of formula I are used as activesubstances in which R represents a benzyl radical optionally substitutedby halogen and/or NO- or a phenyl radical having 4 or 5 substituentsselected from halogen, an alkyl, alkoxy and/or nitro group or a 5- to6-membered heterocyclic radical that is bound over an alkyl radical.

As examples of especially active group for combating bacteria and fungithose of compound II may be mentioned:

Among these, the compounds of the formulae CF: C1 (31 Cl NH-C 0- 0- -01and CF; 01 Cl 01- -NHCO0 01 are particularly effective active substancesin combating lower organisms.

To the particularly effective type of compound there moreover belongthose of the formula (III) C1 NHCOOCHz(CH=CH)nR in which n=0 or 1 and Rrepresents an aromatic radical.

The active substances of formula (I) have an outstanding effectivenessagainst plant-pathogenic bacteria and fungi, e.g. Piricularia oryzae(rice blast). In addition to these properties they have a considerableeffect against insects, for example soil insects or storage pests,against gastropodes, nematodes, particularly plant nematodes, such asPanagrellus redivivus, and can be used in certain concentrations againstundesirable plants. They also show an activity against human and animalpathogenic helminths, for example trematodes and cestodes, as well asagainst arachnoids (spiders, mites, ticks etc.).

The compounds of formula (I) may be prepared by the methods known forthe preparation of carbamates by reacting araliphatic or heterocyelichydroxyl compounds or phenols of the formula HO-R (a) with para-chlorometa trifiuoromethylphenyl isocyanate in substance, in protected form(as adduct with NaHSO or in situ,

(b) or with para-chloro-meta-trifluoromethylphenyl carbamic acid halideobtained by reacting parachlorometa-trifluoroaniline and haloformic acidester.

The active substances of the present invention have antimicrobic,particularly antibacterial properties, for example against Gram-positiveorganisms, such as Staph. aureus as well as against acid-resistantbacteria, such as M. tuberculosis.

In aqueous dispersion they have an afiinity for keratin fibres andprotect the treated material from destruction by larvae of smallbutterflies (moths) and certain kinds of coleoptera (for example larvaeof Attagenus or Anthrenus). The carbamates of formula (I) are suitablefor disinfection purposes and for the disinfecting cleaning of articles,for example of cellulose-containing material. Such compounds can beprocessed to textile detergents and toilet soaps.

It is particularly advantageous that the compounds of formula (I) do notshow any toxic side-effects towards warm-blooded animals in theconcentrations required for disinfection. This makes it possible to usethe new compounds for combating harmful organisms on a board basis, forexample for the protection of timber, for preserving various industrialproducts, for protecting fibrous materials against harmfulmicroorganisms, for preserving agricultural products, as disinfectantsin veterinary medicine, in general hygiene and body care.

It is of particular importance that the compounds of the invention donot lose their bactericidal and fungicidal activity in the presence ofalbuminous substances and soaps. The new compounds do not have anobjectionable odor of their own and are well tolerated, at least byhealthy skin.

Among the industrial products which may be preserved and/or disinfectedwith the help of the disinfectants according to the invention, thefollowing may be selected as examples: textile assistants or finishingagents, glues, binders, paints, thickeners, dyeing or printing pastesand similar preparations based on organic and inorganic dyestuffs orpigments, including those which contain casein or other organiccompounds as admixtures. Wall and ceiling paints, for example thosecontaining an albuminous colour binder, are also protected againstattack by pests by adding the new compounds.

Furthermore, the new compounds may be used for the protection of fibresand textiles by being absorbed on natural or synthetic fibres and theredeveloping a durable action against harmful organisms, for examplefungi, bacteria and insects. The compounds may be added before,simultaneously, or after treatment of these textiles with othersubstances, for example dyeing or printing pastes, finishing agents andthe like. The compounds are in special measure able to protect Woolfibres against moths and other ingestion pests. They show, for example,an excellent activity against moth larvae when applied to the fibre froman acetone solution or after absorption on the fibre from an aqueousbath in the presence of an emulsifier.

The compounds of formula (I) may also be used as preservatives in thecellulose and paper industry, inter alia for preventing the known slimeformation caused by microorganisms in the apparatus used for theproduction of paper.

Depending on the nature of the additives with which the new activesubstances are combined in the agents according to the invention,preparations are obtained which are especially suitable for cleaning,disinfection or body care.

Thus, for example, detergents and cleansing agents having an excellentantibacterial or antimycotic effect are obtained by combining thecompounds according to the invention with detergents and/orsurface-active substances. The compounds of the formula (I) may, forexample, be incorporated into soaps or be combined with soap-freedetergents and/or surface-active substances, or they may be combinedwith mixtures of soaps and soapfree detergents.

The invention relates therefore also to the use of detergents andcleansing agents which contain as active component a compound of formula(I), and also to making textile and non-textile materialsbacteria-resistant.

In most cases textile materials of synthetic or natural origin areprotected against infestation by bacteria by a content of 0.1 to 3% ofactive substance. The active substance may be used together with othertextile assistants, such as finishing agents, anti-creasing dressingsetc.

The preparations of the invention that contain the compounds of formula(I) may also be employed as cleansing agents in industry or in thehousehold, as well as in the food industry, e.g. dairies, breweries,abattoirs, in agriculture and in veterinary hygiene.

In general, the application forms correspond to the ordinaryformulations of pesticides; for example preparations that contain thecompounds of formula (I) may also contain additives such as carriers,solvents, diluents, dispersants, wetting agents or adhesives as well asother pesticides.

The following Examples illustrate the invention.

EXAMPLE 1 75 parts by weight of pentachlorphenol in 300 parts by volumeof acetonitrile and 67 parts by weight ofp-chlorom-trifiuoromethylphenyl isocyanate in 100 parts by volume ofacetonitrile are mixed at 50 C. and 0.1 part of triethylenediamine isadded. The reaction mixture is allowed to stand for 3 hours at roomtemperature, then cooled and the product obtained is filtered 01f.

Compound No. 1

Melting point: 162-164 C. (from toluene).

In an analogous manner the following compounds of the type CF;ClNH-C00-R1 may be prepared:

Meltlng R1 Compound number:

2 C1 Cl 143-145 4 OzN Cl 151-153 Q-OCH:

Br Br Bl CH3 12- (E a-(1H2 113-115 -OHz-CH CH TABLEContinued Meltiintg on R; C.

Compound number:

--CHr-LO 17 Oil -CH -CH=CH 1 Deeomposed.

EXAMPLE 2 In a greenhouse cucurbita pepo L. plants were grown andsprayed once prophylactically with an aqueous broth of the test-productcontaining 0.1% of active substance of the compound 3. Two days aftertreatment the plants were infected with spores of Erysiphecz'choriacearum DC and after 12 to 14 days inspected as to infestationwith fungi. In comparison with the untreated control (0% effect) theeffect on the sprayed plants was 100% without phytotoxicity.

EXAMPLE 3 The new carbamates of the formula (I) show a pronounced,strong effect against Gram-positive bacteria, particularly againstStaphylococci and streptococci. They are also effective againstpathogenic fungi, for example T rz'chophyton interdigitale.

The antibacterial activity in the dilution test was determined asfollows:

Bacteriostasis and bacteriocidal activity Bacteriostatic/cidal CompoundStaph. aureus Each. col

EXAMPLE 4 In order to test the antimycotic effect a solution of 1%strength of an active compound in propylene-glycol was prepared anddiluted with a beer-wort solution in concentrations of 250, 100, 50, 30,10, 3, l and 0.5

p.p.m. The determination of the fungistatic limit concentration gave thefollowing values in p.p.m.:

Aspar- In order to test the effect on gastropodes the following aqueousdilution series of an active substance concentration was prepared: 25,12, 6, 4, 3, 2 and 1 p.p.m. Batches of 5 snails each (Australorbisglabratus) having a shell diameter of 15 mm. were put into each of thesesolutions for 24 hours at 20-22 C. They were then taken out and put fora further 48 hours in clear water with the addition of food. After thisrecuperation time the lethal rate was determined. For compound 1 thelethal rate was 100% in a concentration of 1.5 p.p.m.

EXAMPLE 6 In order to test the insecticidal effect young Phaseolusplants were dipped into aqueous active substance solutions containing0.2%, 0.1%, 0.08%, 0.04% and 0.02% of active substance, allowed to dryand infested with 5 larvae each of Orgia gonostigma in the L-3 stage or5 larvae each of Epilachna varivestis in the L4 stage; the whole of eachof the plants then being covered with a plastic bag. The followingresults were obtained:

Mortalities with a concentration of 0.08% active substance Time,Mortality,

Larvae days percent;

Compound number:

- Orgyia 5 17 d0 5 Epilachna 6 80 EXAMPLE 7 FORMULATION EXAMPLES Dustingpreparations Equal parts of an active substance according to theinvention and precipitated silicic acid are finely ground. By mixingwith kaolin or talcum, dusting preparations can be prepared containingpreferably 1-6% of active substance.

Spraying powders For the preparation of a spraying powder the followingcomponents are, for example, mixed and finely ground:

50 parts of active substance according to the present invention 20 partsof Hi-Sil (highly adsorbant silicic acid) 25 parts of bolus alba(kaolin) 3.5 parts of the reaction product from para-tertiaryoctylphenol and ethyleneoxide 1.5 parts of (sodium1-benzyl-2-stearyl-benzimidazole- 6,3'-disulphonate) Emulsionconcentrates Readily soluble active substances may also be formulated asemulsion concentrates according to the following prescriptions:

20 parts of active substance 70 parts of xylene 10 parts of a mixturefrom a reaction product of an alkylphenol with ethyleneoxide and calciumdodecylbenzene sulphonate are mixed. On being diluted with water to thedesired concentration a sprayable emulsion is formed.

We claim:

1. A method of combatting Gram-positive bacteria and fungi whichcomprises applying to an area infested with said bacteria and fungi abactericidally and fungicidally effective amount of a compound of theformula 3. A method according to claim 1 in which the compound is CF:(ll-@NH-CO-O- 4. A method according to claim 1 in which the compound isOaN Cl 5. A method according to claim 1 in which the compound is CF:crQ-mr-oo-o 6. A method for combatting plant pathogenic fungi whichcomprises applying to plants infested with said fungi a fungicidallyeffective amount of a compound of the formula l Zn wherein n is aninteger of 4 to 5 and Z represents substituents which may be the same ordifferent from one another and which are selected from the groupconsisting of methyl, methoxy, chlorine, bromine and nitro, at leastthree of said substituents being selected from the group consisting ofchlorine and bromine.

7. A method according to claim 6 in which the com pound is CF; Cl

8. A method of combating bacteria and fungi which comprises applying toan area infested with bacteria and fungi a bactericidally andfungicidally effective amount of the compound of the formula 9. AGram-positive bactericidal and fungicidal composition comprising (1) asactive ingredient an effective amount of a compound of the formulawherein n is an integer of 4 or 5, and Z represents substituents whichmay be the same or different from one another and which are selectedfrom the group consisting of methyl, methoxy, chlorine, bromine andnitro, at least three of said substituents being selected from the groupconsisting of chlorine and bromine, and (2) a suitable carrier.

References Cited UNITED STATES PATENTS 3,676,457 7/1972 Hubele et al260471 3,308,018 3/1967 Gier 260 471 ALBERT T. MEYERS, Primary ExaminerL. SCHENKMAN, Assistant Examiner US. Cl. X.R. 424-263, 285

